Toward Accurate Conformational Energies of Smaller Peptides and Medium-Sized Macrocycles: MPCONF196 Benchmark Energy Data Set,Journal of Chemical Theory and Computation

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Toward Accurate Conformational Energies of Smaller Peptides and Medium-Sized Macrocycles: MPCONF196 Benchmark Energy Data Set
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-02-20 00:00:00 , DOI: 10.1021/acs.jctc.7b01074
Jan Řezáč ₁ , Daniel Bím ₁ , Ondrej Gutten ₁ , Lubomír Rulíšek ₁

Affiliation

A carefully selected set of acyclic and cyclic model peptides and several other macrocycles, comprising 13 compounds in total, has been used to calibrate the accuracy of the DFT(-D3) method for conformational energies, employing BP86, PBE0, PBE, B3LYP, BLYP, TPSS, TPSSh, M06-2X, B97-D, OLYP, revPBE, M06-L, SCAN, revTPSS, BH-LYP, and ωB97X-D3 functionals. Both high- and low-energy conformers, 15 or 16 for each compound adding to 196 in total, denoted as the MPCONF196 data set, were included, and the reference values were obtained by the composite protocol, yielding the CCSD(T)/CBS extrapolated energies or their DLPNO-CCSD(T)/CBS equivalents in the case of larger systems. The latter was shown to be in near-quantitative (∼0.10–0.15 kcal·mol^–1) agreement with the canonical CCSD(T), provided the TightPNO setting is used, and, therefore, can be used as the reference for larger systems (likely up to 150–200 atoms) for the problem studied here. At the same time, it was found that many D3-corrected DFT functionals provide results of ∼1 kcal·mol^–1 accuracy, which we consider as quite encouraging. This result implies that DFT-D3 methods can be, for example, safely used in efficient conformational sampling algorithms. Specifically, the DFT-D3/DZVP-DFT level of calculation seems to be the best trade-off between computational cost and accuracy. Based on the calculated data, we have not found any cheaper variant for the treatment of conformational energies, since the semiempirical methods (including DFTB) provide results of inferior accuracy (errors of 3–5 kcal·mol^–1).

中文翻译：

迈向小肽和中型大环化合物的准确构象能：MPCONF196基准能量数据集

精心选择的一组无环和环状模型肽以及其他几个大环（总共包含13种化合物）已被用于校准BP86，PBE0，PBE，B3LYP，BLYP的DFT（-D3）方法用于构象能量的准确性，TPSS，TPSSh，M06-2X，B97-D，OLYP，revPBE，M06-L，SCAN，revTPSS，BH-LYP和ωB97X-D3功能。高能和低能构象异构体，每种化合物总共15或16，共计196个，表示为MPCONF196数据集，并通过复合方案获得参考值，得出CCSD（T）/ CBS如果是大型系统，则外推能量或它们的DLPNO-CCSD（T）/ CBS等效值。后者显示为接近定量的（〜0.10–0.15 kcal·mol ^–1）与规范的CCSD（T）一致，前提是使用了TightPNO设置，因此，对于此处研究的问题，它可以用作较大系统（可能多达150–200个原子）的参考。同时，发现许多D3校正的DFT功能提供的结果约为1 kcal·mol ^–1准确性，我们认为这非常令人鼓舞。该结果表明，例如，DFT-D3方法可以安全地用于有效的构象采样算法中。具体来说，DFT-D3 / DZVP-DFT的计算级别似乎是计算成本和准确性之间的最佳折衷方案。根据计算得出的数据，由于半经验方法（包括DFTB）提供的准确性较低的结果（3–5 kcal·mol ^–1的误差），因此我们没有发现任何更便宜的构象能量变体。

更新日期：2018-02-20

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